CN104822798A - Luminescent quantum dot - Google Patents
Luminescent quantum dot Download PDFInfo
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- CN104822798A CN104822798A CN201380062093.4A CN201380062093A CN104822798A CN 104822798 A CN104822798 A CN 104822798A CN 201380062093 A CN201380062093 A CN 201380062093A CN 104822798 A CN104822798 A CN 104822798A
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- 0 C*c1c(cccc2)c2c(-c2ccccc2)c2c1cccc2 Chemical compound C*c1c(cccc2)c2c(-c2ccccc2)c2c1cccc2 0.000 description 1
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Abstract
The present invention relates to a luminescent quantum dot, and more particularly, to a quantum dot of which ligand for capping the quantum dot includes a light-emitting material and which has excellent dispersibility and stability in an aqueous solution and has high color purity and light-emitting properties when applied in a light-emitting device, and to a method for manufacturing same.
Description
Technical field
The present invention relates to a kind of luminescent quantum dot, the part particularly relating to coated (capping) quantum dot contains luminophore, thus not only dispersiveness in aqueous and stability remarkable, and when being applicable to luminous element the preparation method of purity of color and the excellent luminescent quantum dot of the characteristics of luminescence and this luminescent quantum dot.
Background technology
Quantum dot (Quantum Dot) is the semiconductor substance of nanosized, it illustrates quantum limit (quantum confinement) effect, and with regard to this quantum dot, if reach energy excited state from excitaton source (excitationsource) light, then discharge the energy of corresponding band gap (bandgap) voluntarily.In addition, if the size of quantum point and regulate corresponding band gap, then can regulate electricity, optical characteristics, thus only the size of quantum point just can regulate emission wavelength, and the characteristics such as excellent purity of color and high-luminous-efficiency can be shown, therefore, quantum dot can be applied to the Various Components such as luminous element or photo-electric conversion element.
With regard to now worked out as luminous element quantum dot with regard to, because dispersed and stability reduces in aqueous, and purity of color and the characteristics of luminescence reduce, be thus difficult to be used as luminous element, practical situation to carry out the research for quantum dot by persistence.
Summary of the invention
Technical problem
In order to solve problem as above, the present invention its object is to provide the preparation method of a kind of luminescent quantum dot, this luminescent quantum dot and comprise the luminous element of this luminescent quantum dot, wherein, described luminescent quantum dot not only dispersiveness in aqueous and stability remarkable, and when being applicable to luminous element purity of color and the characteristics of luminescence excellent.
To deal with problems scheme
In order to achieve the above object, the invention provides a kind of quantum dot, this quantum dot is for comprising core/shell (core/shell) structure and being attached to the quantum dot of part on shell surface, and above-mentioned part comprises luminophore.
In addition, the invention provides a kind of preparation method of luminescent quantum dot, the preparation method of described luminescent quantum dot is characterized in that, carries out the step stirred after being included in the solution being dispersed with core/shell structures the part added containing luminophore.
In addition, the present invention, in luminous element, provides a kind of and it is characterized in that comprising above-mentioned luminescent quantum dot and as the luminous element of luminophore.
In addition, the present invention, in the preparation method of luminous element, provides a kind of preparation method that it is characterized in that comprising the luminous element forming the step of luminescent layer with above-mentioned luminescent quantum dot.
Invention effect
Luminescent quantum dot according to the present invention due to not only dispersiveness in aqueous and stability remarkable, and when being applicable to luminous element purity of color and the characteristics of luminescence excellent, thus can have the purity of color, high stability and the high-luminous-efficiency that are better than existing luminous element.
Accompanying drawing explanation
Fig. 1 shows the preparation method of the quantum dot (QD) according to one embodiment of the invention.
Fig. 2 illustrates the mode chart of the luminous element of the luminescent quantum dot that make use of according to one embodiment of the invention.
Fig. 3 determines UV (ultraviolet) absorption of luminescent quantum dot according to an embodiment of the invention and the result of PL (photoluminescence) spectrum.
Fig. 4 determines UV (ultraviolet) absorption of luminous element according to an embodiment of the invention and the result of PL (photoluminescence) spectrum.
Fig. 5 is IVL (current-voltage-brightness) characteristic of electroluminescent (EL) element determined according to one embodiment of the invention and the result of EL spectrum.
Fig. 6 shows the chromaticity coordinates of electroluminescent (EL) element according to one embodiment of the invention.
Embodiment
Below describe the present invention in detail.
Luminescent quantum dot of the present invention, it is the quantum dot of the part comprising core/shell structures and be attached to shell surface, and described luminescent quantum dot is characterized in that, above-mentioned part comprises luminophore.
Above-mentioned part comprises luminophore and the linking group being connected shell and luminophore, and can comprise spacer between linking group and luminophore as required.
Following structural formula 1 shows the mode chart of the luminescent quantum dot according to one embodiment of the invention.
Structural formula 1
In structure above 1, A represents luminophore, and L represents spacer, and X represents linking group.In the present invention, above-mentioned luminophore can be identical or different independently of one another, and can send the light of identical color or send the light of two or more different color.
In luminescent quantum dot of the present invention, core/shell structures can use known core/shell structures, as an example, can also utilize core/shell structures described in No. 2010-35466th, Korean Patent Laid.More particularly, core/shell structures can enumerate by a) be selected from the 2nd race, the 12nd race, the 13rd race and the 14th race the first element and be selected from the second element of the 16th race; B) be selected from the first element of the 13rd race and be selected from the second element of the 15th race; And, c) a kind of material selected in the group that the 14th race's element forms or their core/shell structures of being formed, as its example, can be selected from by MgO, MgS, MgSe, MgTe, CaO, CaS, CaSe, CaTe, SrO, SrS, SrSe, SrTe, BaO, BaS, BaSe, BaTE, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe, Al
2o
3, Al
2s
3, Al
2se
3, Al
2te
3, Ga
2o
3, Ga
2s
3, Ga
2se
3, Ga
2te
3, In
2o
3, In
2s
3, In
2se
3, In
2te
3, SiO
2, GeO
2, SnO
2, SnS, SnSe, SnTe, PbO, PbO
2, PbS, PbSe, PbTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, BP, Si, Ge composition group in more than a kind, and the structure of the core/shell morphology that them can be used to be formed.
The mean diameter of above-mentioned core/shell structures can be regulated arbitrarily, and the diameter of 1-12nm can be used.Preferably, send more than 500nm and the core/shell structures of the light of below 800nm wave band can have the diameter of 5-12nm, send more than 400nm and the core/shell structures being less than the light of 500nm wave band can have the diameter of 1-3nm.
In addition, in luminescent quantum dot of the present invention, above-mentioned luminophore can be suitable for and send more than 400nm and the group of the light of below 800nm wave band.
Above-mentioned luminophore can use known luminophore, can use fluorescence or phosphorescence luminophore as an example.More particularly, above-mentioned luminophore can be one of in following FL1 to FL38 or PL1 to PL59.
In following FL1 to FL38 or PL1 to PL59, * is connection portion, and wherein, connection portion can be connected with more than in the position of substitution in parantheses, and R1 to R16 is hydrogen independently of one another; Heavy hydrogen; Halogen; Amino; Itrile group; Nitro; With heavy hydrogen, halogen, amino, itrile group, the substituted or unsubstituted C of nitro
1~ C
40alkyl; C
2~ C
40thiazolinyl; C
1~ C
40alkoxyl group; C
3~ C
40cycloalkyl; C
3~ C
40heterocyclylalkyl; C
6~ C
40aryl; C
3~ C
40heteroaryl; C
3~ C
40aralkyl; C
3~ C
40aryloxy; C
3~ C
40arylthio or Si.More than 2 optional from R1 to R16 can be combined with each other and form ring, and can comprise S, N, O, Si.
In above-mentioned luminescent quantum dot, as long as above-mentioned linking group can be attached to shell and the connection base be connected with luminophore or spacer is then not particularly limited, as an example, more than a kind base in the group being selected from and being made up of mercaptan (thiol) base, carboxyl, amido, phosphine (phospine) base and phosphide (phosphide) base can be used.The preferred thiol group of above-mentioned connection base.
In addition, in luminescent quantum dot of the present invention, between above-mentioned luminophore and linking group, spacer can be comprised further.Above-mentioned spacer increase can be attached to the luminophore number of core/shell structures, and the part containing luminophore can be made easily to carry out for the dispersion of solvent when preparing luminescent quantum dot, and stop energy trasfer (energy transfer), thus specific implementation high purity white can be contributed to.Specifically, above-mentioned spacer can use substituted or unsubstituted saturated or unsaturated C
1~ C
30alkyl, C
3~ C
40cycloalkyl, Si
1~ Si
30silane, but to be not limited thereto.
It is desirable that luminophore, spacer and linking group are all included in quantum dot of the present invention, as an example, can be following structure.In following each structure, the H part of-SH, COOH, NH is the part be combined with core/shell structures.
In the present invention, the size containing the whole luminescent quantum dot of luminophore at end can regulate arbitrarily, and described size is preferably 5nm to 30nm, is more preferably 10nm-20nm.In addition, in the present invention, the luminous intensity of core/shell structures and luminophore can regulate arbitrarily, in the present invention when core/shell structures and luminophore are in complementary color relation, from as white light source angle, preferably it differs within 30% the intensity ratio of core/shell structures and luminophore.Such as, at more than 400nm and the luminous intensity being less than 500nm wave band is 1 time, more than 500nm and the luminous intensity of below 800nm wave band is preferably 0.7-1.3, at more than 500nm and the luminous intensity of below 800nm wave band is 1 time, more than 400nm and the luminous intensity being less than 500nm wave band is preferably 0.7-1.3.
Following structural formula 2 shows the mode chart of the luminescent quantum dot according to a concrete example of the present invention, and luminophore sends more than 400nm and is less than the light of 500nm wave band, and core/shell structures can use known quantum dot.
Structural formula 2
Carry out the step that stirs can be included in the solution being dispersed with core/shell structures the part added containing luminophore according to luminescent quantum dot of the present invention after and prepare.Certainly, the preparation of above-mentioned core/shell structures can use known various method, specifically, can utilize synthetic method described in Fig. 1.
In addition, with regard to comprising the preparation of the part of luminophore, by making linking group be combined with luminophore, or spacer is made to be included between luminophore and linking group can to prepare part through the process of following reaction formula 1 and reaction formula 2.
Reaction formula 1
Reaction formula 2
Above-mentioned reaction formula 2 can be specifically following reaction formula 3.
Reaction formula 3
In above-mentioned each reaction formula, A, L, X with structural formula 1 define identical.
In addition, be attached to by the part containing luminophore in the method for core/shell structures, above-mentioned stirring can be carried out 0.1 to 100 hour at the temperature of normal temperature to 100 DEG C.
In addition, the invention provides and a kind ofly make use of the luminous element (QLED) of above-mentioned luminescent quantum dot and the preparation method of this luminous element.In the present invention, with regard to above-mentioned luminous element, except the luminescent layer that use is formed according to above-mentioned luminescent quantum dot of the present invention, certainly can be suitable for other known technology.
As an example, according to an embodiment, the mode that luminous element can be formed successively with the luminescent layer-anode of substrate-negative electrode-utilize luminescent quantum dot according to the present invention to be formed is formed, and electron transfer layer can be formed further between above-mentioned negative electrode and luminescent layer, and between luminescent layer and anode, hole transmission layer can also be formed further.In addition, hole inhibition layer can also be comprised further between electron transfer layer and luminescent layer as required, and buffer layer (buffer layer) can also be formed between the layers.
In the present invention, the luminous element (QLED) utilizing common making method just can be formed to make use of luminescent quantum dot, and the thickness containing each organic membrane of above-mentioned luminescent layer can make 30nm to 100nm.
Buffer layer can be formed between the layers in luminous element according to the present invention, and can use as the starting material of this buffer layer the material usually used, such as can use copper phthalocyanine (copperphthalocyanine), Polythiophene (polythiophene), polyaniline (polyaniline), polyacetylene (polyacetylene), polypyrrole (polypyrrole), p-phenylene vinylene (polyphenylene vinylene) or their derivative, but be not limited thereto.
Starting material as above-mentioned hole transmission layer can use the material usually used, such as, can use poly-triphenylamine (polytriphenyl amine), but be not limited thereto.
Starting material as above-mentioned electron transfer layer can use the material usually used, such as, can use polyoxadiazoles (polyoxadiazole), but be not limited thereto.
Starting material as above-mentioned hole inhibition layer can use the material usually used, such as, can use LiF, BaF
2or MgF
2deng, but be not limited thereto.
More particularly, luminous element of the present invention can also be prepared according to method described in Fig. 2.
Prepare as described above according to luminous element of the present invention, stability is high and have the purity of color and high-luminous-efficiency that are better than existing luminous element.
Below, point out preferred embodiment to contribute to understanding the present invention, but following embodiment just illustrates the present invention, scope of the present invention is not limited to following embodiment.
The synthesis (synthesis of luminophore) of the bromo-10-phenylanthracene of [synthesis example 1] 9-
Under argon or nitrogen environment, 2-naphthalene boronic acids 4.2g, 9-bromine anthracene 6.8g, tetrakis triphenylphosphine palladium (0) 0.6g, toluene 50ml and sodium carbonate 8.4g being dissolved in and joining capacity after in water 50ml is in the flask of 250ml, and carries out backflow heated and stirred 24 hours.After reaction terminates, the crystal of separating out for being cooled to room temperature has carried out filtering separation.With toluene, recrystallization is carried out to this and obtains 7.5g crystal.
Under argon or nitrogen environment, by above-mentioned crystal 7.5g with to join capacity through DMF (dimethyl formamide) 100ml of processed be in the flask of 250ml, and carry out heating with 80 DEG C of temperature and after making material dissolution, at 50 DEG C of temperature, add N-bromosuccinimide 4.8g and stirred 2 hours.After reaction terminates, the crystal of separating out for injecting reaction solution in 200ml Purified Water has carried out filtering separation.With toluene, recrystallization is carried out to this and obtains 6.8g crystal.
[synthesis example 2] 9-(10-bromo decyl)-10-phenylanthracene (synthesis of spacer)
Bromo-for 9-10-phenylanthracene 8g is dissolved in anhydrous diethyl ether (anhydrous diethyl ether) 300ml.Here, at 0 DEG C, n-BuLi (2M) 18ml is added lentamente.1,10-dibromo-decane 21.6ml is added maintain 1 hour at 0 DEG C after.Carry out 2 hours reflux after 30 minutes to stir.Reaction is cooled to normal temperature and adds distilled water 80ml when no longer carrying out.With 40ml ether, 3 extractions are carried out to water layer after collected organic layer.After removing moisture with anhydrous magnesium sulfate, hexane (hexane) is carried out post as moving phase and has been isolated grass green oily 9-(10-bromo decyl)-10-phenylanthracene 5.7g (50%).
1H NMR(CDCl
3,400MHz):8.32(2H,d),7.63(2H,d),7.59(9H,m),3.92(2H,t),3.65(2H,t),1.70-1.68(2H,m),1.64-1.60(4H,m),1.52(10H,m)
The synthesis of [synthesis example 3] Compound D J-A-1
9-(10-bromo decyl)-10-phenylanthracene 4g (1eq) and thiocarbamide 1.3g (2eq) to be dissolved in dehydrated alcohol 50ml and carried out 4 hours reflux and stir.Here add the sodium hydroxide 50ml of 6M and carried out 2 hours reflux stirrings.Remove ethanol when reaction is no longer carried out and carried out 3 extractions with 30ml ethyl acetate.After salt brine solution cleaning, and after removing moisture with anhydrous magnesium sulfate, by CHCl
3carry out post as moving phase and be isolated grass green oily 10-(10-phenylanthracene-9-base) decane-1-mercaptan (10-(10-phenylanthrace-9-yl) decane-1-thiol) 1.4g (39%).
1H-NMR(CDCl
3,Varian400MHz):δ1.26-1.38(6H,m),1.43-1.46(4H,m),1.62-1.66(2H,m),1.85-1.90(4H,m),3.42(2H,t,J=6.8Hz),3.64-3.69(2H,m),7.31-7.35(2H,m),7.40-7.42(2H,m),7.48-7.59(5H,m),7.66(2H,d,J=8.8Hz),8.33(2H,d,J=9.2Hz)。
LC-MS (LC:Agilent 1200, MS:LCQ Advantage Max): moving phase is from 0% [water+0.01%HFBA+1.0%IPA] and 100% [CH
3cN+0.01%HFBA+1.0%IPA] to 0% [water+0.01%HFBA+1.0%IPA] and 100% [CH
3cN+0.01%HFBA+1.0%IPA] use 6.0min).Purity is 99.72%, Rt=2.48min; MSCalcd.:426.24; MSFound 426.2 [M].
The synthesis of [synthesis example 4] Compound D J-A-2
Be repeated the process of above-mentioned synthesis example 1 to synthesis example 3, and in synthesis example 2, replace 1,10-dibromo-decane and employ pentamethylene bromide (1,5-dibrompentane), synthesize light yellow (Paleyellow) DJ-A-2.
1H-NMR(CDCl
3,Varian400MHz):δ1.45(1H,t,J=7.6Hz),1.74-1.81(4H,m),1.87-1.92(2H,m),2.60(2H,q,J=7.6Hz),3.66-3.70(2H,m),7.32-7.35(2H,m),7.40-7.42(2H,m),7.48-7.54(3H,m),7.55-7.59(2H,m),7.66(2H,d,J=8.4Hz),8.31(2H,d,J=8.8Hz)。
LC-MS (LC:Agilent 1200, MS:LCQ Advantage Max): moving phase is from 10% [water+0.01%HFBA+1.0%IPA] and 90% [CH
3cN+0.01%HFBA+1.0%IPA] to 5% [water+0.01%HFBA+1.0%IPA] and 95% [CH
3cN+0.01%HFBA+1.0%IPA] use 6.0min).Purity is 99.52%, Rt=2.61min; MSCalcd.:356.16; MSFound 356.2 [M].
The W-response mode chart of above-mentioned synthesis example 3 and synthesis example 4 is as follows.
The synthesis of [synthesis example 5] Compound D J-A-3
Be repeated the process of above-mentioned synthesis example 1 to synthesis example 3, and in synthesis example 1, replace the bromo-10-phenylanthracene (9-bromo-10-phenylanthracene) of 9-and employ 9-(4-bromophenyl)-10-phenylanthracene (9-(4-bromopheneyl)-10-phenylanthracene), synthesize white solid DJ-A-3.
1H-NMR(CDCl
3,Varian400MHz):δ1.32-1.45(12H,m),1.60-1.63(2H,m),1.75-1.78(2H,m),2.52(2H,q,J=7.6Hz),2.75-2.79(2H,m),7.30-7.32(4H,m),7.35-7.41(4H,m),7.46-7.48(2H,m),7.53-7.61(3H,m),7.66-7.73(4H,m)。
LC-MS (LC:Agilent 1200, MS:LCQ Advantage Max): moving phase is from 0% [water+0.01%HFBA+1.0%IPA] and 100% [CH
3cN+0.01%HFBA+1.0%IPA] to 0% [water+0.01%HFBA+1.0%IPA] and 100% [CH
3cN+0.01%HFBA+1.0%IPA] use 10min).Purity is 99.62%, Rt=3.94min; MSCalcd.:502.27; MSFound 502.2 [M].
The synthesis of [synthesis example 6] Compound D J-A-4
In above-mentioned synthesis example 5, replace 1,10-dibromo-decane and employ pentamethylene bromide (1,5-dibrompentane), having synthesized light yellow (Pale yellow) solid DJ-A-4.
1H-NMR(CDCl
3,Varian400MHz):δ1.39(1H,t,J=7.6Hz),1.54-1.60(2H,m),1.73-1.82(2H,m),2.61(2H,q,J=7.6Hz),2.79-2.82(2H,m),7.31-7.33(4H,m),7.39-7.40(4H,m),7.47-7.49(2H,m),7.54-7.60(3H,m),7.67-7.73(4H,m)。
LC-MS (LC:Agilent 1200, MS:LCQ Advantage Max): moving phase is from 5% [water+0.01%HFBA+1.0%IPA] and 95% [CH
3cN+0.01%HFBA+1.0%IPA] to 0% [water+0.01%HFBA+1.0%IPA] and 100% [CH
3cN+0.01%HFBA+1.0%IPA] use 6.0min).Purity is 99.58%, Rt=2.85min; MSCalcd.:432.19; MSFound 432.2 [M].
The W-response mode chart of above-mentioned synthesis example 5 and synthesis example 6 is as follows.
The synthesis of [synthesis example 7] Compound D J-A-5
Be repeated the process of above-mentioned synthesis example 1 to synthesis example 3, and in synthesis example 1, replace the bromo-10-phenylanthracene (9-bromo-10-phenylanthracene) of 9-and employ the bromo-10-of 9-(2-naphthyl) anthracene (9-borom-10-(2-napthyl) anthracene), synthesize yellow solid DJ-A-5.
1H-NMR(CDCl
3,Varian400MHz):δ1.32-1.42(12H,m),1.59-1.65(2H,m),1.75-1.81(2H,m),2.54(2H,q,J=7.6Hz),2.79(2H,t,J=7.6Hz),7.28-7.35(4H,m),7.39-7.43(4H,m),7.57-7.62(3H,m),7.69-7.76(4H,m),7.90-7.93(1H,m),7.98(1H,s),8.01-8.04(1H,m),8.07(1H,d,J=8.4Hz)。
LC-MS (LC:Agilent 1200, MS:LCQ Advantage Max): moving phase is from 0% [water+0.01%HFBA+1.0%IPA] and 100% [CH
3cN+0.01%HFBA+1.0%IPA] to 0% [water+0.01%HFBA+1.0%IPA] and 100% [CH
3cN+0.01%HFBA+1.0%IPA] use 10min).Purity is 99.84%, Rt=4.95min; MSCalcd.:552.29; MSFound 552.2 [M].
The W-response mode chart of synthesis example 7 is as follows.
The synthesis of [synthesis example 8] Compound D J-A-6
Be repeated the process of above-mentioned synthesis example 7, and in synthesis example 2, replace 1,10-dibromo-decane and employ pentamethylene bromide (1,5-dibrompentane), synthesize yellow solid DJ-A-6.
1H-NMR(CDCl
3,Varian400MHz):δ1.39(1H,t,J=7.2Hz),1.62-1.54(2H,m),1.85-1.71(4H,m),2.61(2H,q,J=7.2Hz),2.83-2.79(2H,m),7.36-7.28(4H,m),7.42(4H,s),7.63-7.59(3H,m),7.76-7.70(4H,m),7.93-7.91(1H,m),7.98(1H,s),8.04-8.02(1H,m),8.07(1H,d,J=8.4Hz)。
LC-MS (LC:Agilent 1200, MS:LCQ Advantage Max): moving phase is from 0% [water+0.01%HFBA+1.0%IPA] and 100% [CH
3cN+0.01%HFBA+1.0%IPA] to 0% [water+0.01%HFBA+1.0%IPA] and 100% [CH
3cN+0.01%HFBA+1.0%IPA] use 6.0min).Purity is 99.76%, Rt=2.23min; MSCalcd.:482.21; MSFound 482.2 [M].
The W-response mode chart of synthesis example 8 is as follows.
[synthesis example 9] 9-(the bromo-9-anthryl of 10-)-N
3, N
3, N
6, N
6the synthesis (synthesis of luminophore) of-tetraphenyl-9H-carbazole-3,6-diamines
Under argon or nitrogen environment, by 2, it is in the flask of 1000ml that 7-bis-bromo-9H-carbazole 32.5g, pentanoic 37.2g, three (dibenzalacetone) palladium (0) 4.6g, toluene 300ml and sodium tert-butoxide 100g join capacity, and carries out backflow heated and stirred 24 hours.After reaction terminates, the crystal of separating out for being cooled to room temperature has carried out filtering separation.With toluene, recrystallization is carried out to this and obtains 40g crystal.
Under argon or nitrogen environment, it is in the flask of 1000ml that above-mentioned crystal 40g, 9-bromine anthracene 38g, three (dibenzalacetone) palladium (0) 2.2g, toluene 400ml and sodium tert-butoxide 60g are joined capacity, and carries out backflow heated and stirred 24 hours.After reaction terminates, the crystal of separating out for being cooled to room temperature has carried out filtering separation.With toluene, recrystallization is carried out to this and obtains 45g crystal.
Under argon or nitrogen environment, by above-mentioned crystal 45g with to join capacity through DMF (dimethyl formamide) 500ml of processed be in the flask of 1000ml, and carry out heating with 80 DEG C of temperature and after making material dissolution, at 50 DEG C of temperature, add N-bromosuccinimide 15g and stirred 2 hours.After reaction terminates, the crystal of separating out for injecting reaction solution in 200ml Purified Water has carried out filtering separation.With toluene, recrystallization is carried out to this and obtains 42g crystal.
[synthesis example 10] 9-(10-bromo decyl-9-anthryl)-N
3, N
3, N
6, N
6the synthesis (synthesis of spacer) of-tetraphenyl-9H-carbazole-3,6-diamines
By 9-(the bromo-9-anthryl of 10-)-N
3, N
3, N
6, N
6-tetraphenyl-9H-carbazole-3,6-diamines 9.5g dissolves in anhydrous diethyl ether (anhydrous diethyl ether) 300ml.Here, at 0 DEG C, n-BuLi (2M) 17.5ml is added lentamente.1,10-dibromo-decane 22.4ml is added maintain 1 hour at 0 DEG C after.Carry out 2 hours reflux after 30 minutes to stir.Reaction is cooled to normal temperature and adds distilled water 80ml when no longer carrying out.With 40ml ether, 3 extractions are carried out to water layer after collected organic layer.After removing moisture with anhydrous magnesium sulfate, hexane (hexane) is carried out post as moving phase and has been isolated grass green oily 9-(10-bromo decyl-9-anthryl)-N
3, N
3, N
6, N
6-tetraphenyl-9H-carbazole-3,6-diamines 6.3g (49%).
1H NMR(CDCl
3,400MHz):8.32(2H,d),8.17(2H,s),7.89(4H,m),7.63(2H,d),7.59(14H,m),3.92(2H,t),3.65(2H,t),1.70-1.68(2H,m),1.64-1.60(4H,m),1.52(10H,m)
The synthesis of [synthesis example 11] Compound D J-A-7
By 9-(10-bromo decyl-9-anthryl)-N
3, N
3, N
6, N
6-tetraphenyl-9H-carbazole-3,6-diamines 4.1g (1eq) and thiocarbamide 1.2g (2eq) to dissolve in dehydrated alcohol 50ml and have carried out 4 hours reflux and stir.Here add the sodium hydroxide 50ml of 6M and carried out 2 hours reflux stirrings.Remove ethanol when reaction is no longer carried out and carried out 3 extractions with 30ml ethyl acetate.After salt brine solution cleaning, and after removing moisture with anhydrous magnesium sulfate, by trichloromethane (CHCl
3) carried out post as moving phase and be isolated grass green oily 10-(10-phenylanthracene-9-base) decane-1-mercaptan (10-(10-phenylanthrace-9-yl) decane-1-thiol) 1.4g (36%).
1H NMR(CDCl
3,400MHz):8.32(2H,d),8.17(2H,s),7.89(4H,m),7.63(2H,d),7.59(14H,m),3.92(2H,t),3.65(2H,t),1.70-1.68(2H,m),1.63-1.60(4H,m),1.51(10H,m)
The synthesis of [synthesis example 12] Compound D J-A-8
Be repeated the process of above-mentioned synthesis example 1 to synthesis example 3, and in synthesis example 2, replace 1,10-dibromo-decane and employ pentamethylene bromide (1,5-dibrompentane), synthesize light yellow (Paleyellow) DJ-A-8.
1H NMR(CDCl
3,400MHz):8.31(2H,d),8.18(2H,s),7.98(4H,m),7.73(2H,d),7.59(14H,m),3.94(2H,t),3.65(2H,t),1.70-1.68(2H,m),1.63-1.60(4H,m),1.51(5H,m)
The W-response mode chart of above-mentioned synthesis example 10 and synthesis example 12 is as follows.
The synthesis of [synthesis example 13] Compound D J-A-9
Be repeated the process of above-mentioned synthesis example 1 to synthesis example 3, and in synthesis example 11, replace 9-(the bromo-9-anthryl of 10-)-N
3, N
3, N
6, N
6-tetraphenyl-9H-carbazole-3,6-diamines and employ 9-(10-(4-bromophenyl)-9-anthryl)-N
3, N
3, N
6, N
6-tetraphenyl-9H-carbazole-3,6-diamines, has synthesized white solid DJ-A-9.
1H NMR(CDCl
3,400MHz):8.32(2H,d),8.17(2H,s),7.89(8H,m),7.63(2H,d),7.59(14H,m),3.92(2H,t),3.65(2H,t),1.70-1.68(2H,m),1.63-1.60(4H,m),1.51(10H,m)
The synthesis of [synthesis example 14] Compound D J-A-10
In above-mentioned [synthesis example 13], replace 1,10-dibromo-decane and employ pentamethylene bromide (1,5-dibrompentane), having synthesized light yellow (Pale yellow) solid DJ-A-10.
1H NMR(CDCl
3,400MHz):8.42(2H,d),8.24(2H,s),7.79(8H,m),7.68(2H,d),7.57(14H,m),3.92(2H,t),3.63(2H,t),1.74-1.68(2H,m),1.63-1.60(4H,m),1.49(10H,m)
The W-response mode chart of above-mentioned synthesis example 13 and synthesis example 14 is as follows.
The synthesis of [synthesis example 15] CdSe/ZnS
0.4mmolCDO (99.99%), the zinc acetate 4mmol of Cadmium oxide (99.9%, powder) and oleic acid (OA) 5.58mL joined in 3 mouthfuls of flasks of 100mL, and under nitrogen environment with the heating temperatures of 150 DEG C 30 minutes.Then, add 1-octadecylene (1-octadecene, ODE) 20mL and temperature is increased to 310 DEG C.3mL tri octyl phosphine (trioctylphosphine, TOP), 1mmol selenium (SE), 2.3mmol sulphur (S) is filled with fast in flask.Temperature of reaction is cooled to normal temperature after 310 DEG C maintain 10 minutes.With 20mL chloroform and excessive acetone purifying the quantum dot generated (more than 3 times).By quantum dot with the concentration redispersion (redispersed) of 5.0mg/mL in chloroform or hexane.
The synthesis of [synthesis example 16] ZnO nanoparticles (Zinc oxide nanoparticle)
ZnO (zinc oxide) nano particle is used for electron transfer layer, and the synthesis of ZnO nano particle employs normally used following method.Namely, zinc acetate (Zinc acetate) is joined dimethyl sulfoxide (DMSO) (dimethylsulfoxide, DMSO, 0.5M) in 30ml, and in ethanol Tetramethylammonium hydroxide (TMAH, 0.55M) mixture is stirred 1 hour.After this, carry out centrifugation and clean with ethanol and excessive acetone mixture.By synthesized ZnO nano particle with the concentration of the 30mg/mL dispersion electron transport layer materials be used as LED manufacturing installation in ethanol.
The synthesis (ligand exchange, Ligand Exchange) of [embodiment 1] white quantum dot
CdSe/ZnS solution (0.2ml has been prepared with quantum dot prepared in above-mentioned synthesis example 15,5mg/ml in hexane), and add luminophore (0.5ml, 3mM are in hexane) prepared in above-mentioned synthesis example 3, and 30 minutes are stirred at normal temperatures.In reaction flask, add methyl alcohol (methanol) and after being cured, carrying out centrifugation and prepared white quantum dot.Confirm ligand exchange (Ligand exchange) result with infrared data (IR DATA), and confirm UV absorption and PL spectrum (FT-IR (Fourier transform infrared) spectrum (a) DJ-A-1 of Fig. 3, (b) DJ-A-1+CdSe/ZnS).
The synthesis (ligand exchange, Ligand Exchange) of [embodiment 2] high color purity white quantum dot
CdSe/ZnS solution (0.2ml has been prepared with quantum dot prepared in above-mentioned synthesis example 15,5mg/ml in hexane), and add luminophore (0.5ml prepared in above-mentioned synthesis example 3,3mM is in hexane) and above-mentioned synthesis example 11 in prepared luminophore (0.5ml, 3mM is in hexane), and stirred 30 minutes at normal temperatures.In reaction flask, add methyl alcohol (methanol) and after being cured, carrying out centrifugation and prepared white quantum dot.Confirm ligand exchange (Ligand exchange) result with infrared data (IR DATA), and confirm UV absorption and PL spectrum.
The making of [embodiment 3] QD-LED element
QD-LED be produced on be coated with indium tin oxide glass (ITO/ glass) substrate (sheet resistance (square resistance) <10 Ω/) on.Use ultrasonic wave and with acetone and Virahol, cleaning in 1 minute carried out to ito glass, and having carried out 1 minute Cement Composite Treated by Plasma with argon/oxygen.
With poly-(3,4-ethene dioxythiophene) (poly (3,4-ethylenedioxythiophene)): poly styrene sulfonate (poly (styrene sulfonate)) (PEDOT:PSS, Baytron P AI 4083)=9:1 volume ratio, and after diluting with Virahol, 30 seconds with 4,000rpm spin coating.By the ito glass that applies with PEDOT:PSS with 120 DEG C of hot plate bake 10 minutes in an atmosphere.
To coated substrate with N
2in the glove box of filling, with 3,000rpm spin coating, Polyvinyl carbazole (0.01g/mL of PVK, chlorobenzene), after 30 seconds, has been carried out 30 minutes baking processing to substrate and has been used as hole transmission layer at 180 DEG C of temperature.By the white quantum dot solution prepared by above-described embodiment 1 with 1,500rpm spin coating 20 second as luminescent layer.
Then, by ZnO nano particle (30mg/mL) solution with 1,500rpm spin coating 30 second, and at 150 DEG C of temperature, substrate 30 minutes have been toasted.Finally, this multilayer film substrate is put into high vacuum vapor deposition chamber (background pressure-5 × 10
-6torr) in and evaporation aluminium negative electrode (thickness of cathode, 100nm).
The making of [comparative example 1] orange (Orange) QD-LED element
Replace white quantum dot in embodiment 3 and use orange (Orange) quantum dot (CdSe/ZnO580) and as luminescent layer.
The making of [comparative example 2] blue (Blue) OLED (Organic Light Emitting Diode) element
Replace white quantum dot in embodiment 3 and use above-mentioned synthesis example 3 DJ-A-1 and as luminescent layer.
The UV of the luminous element of above-described embodiment 3 and comparative example 1 and comparative example 2 is absorbed and PL spectrometry shown in Figure 4.In the diagram, a), b), c) comparative example 1, comparative example 2 and embodiment 3 is represented respectively.
In addition, the IVL characteristic of electroluminescent (EL) element of the luminous element of above-described embodiment 3 and comparative example 1 and comparative example 2 and EL spectrometry are shown in following table 1 and Fig. 5.
Table 1
The making of [embodiment 4] high color purity QD-LED element
Made QD-LED element with the method for above-described embodiment 3, the luminous element of alternate embodiment 1 employs the high color purity luminous element of embodiment 2 and has prepared high color purity QD-LED.Fig. 6 shows the chromaticity coordinates of the QD-LED element of above-described embodiment 3 (a) and embodiment 4 (b).
As shown in Figure 6, known with use blue part at orange QD and compared with the element of the white embodiment 3 of specific implementation, the element simultaneously employing the embodiment 4 of blue part and green part at orange QD illustrates the white of more high color purity.
Industrial utilizability
Luminescent quantum dot according to the present invention due to not only dispersiveness in aqueous and stability remarkable, and when being applicable to luminous element purity of color and the characteristics of luminescence excellent, thus can have the purity of color, high stability and the high-luminous-efficiency that are better than existing luminous element.
Claims (13)
1. a luminescent quantum dot, it is the quantum dot of the part comprising core/shell structures and be attached to shell surface, and wherein, above-mentioned part comprises luminophore.
2. luminescent quantum dot according to claim 1, is characterized in that,
Above-mentioned part comprises luminophore and the linking group being connected shell and luminophore.
3. luminescent quantum dot according to claim 2, is characterized in that,
Above-mentioned part comprises spacer further between above-mentioned linking group and luminophore.
4. luminescent quantum dot according to claim 1, is characterized in that,
Above-mentioned luminophore is selected from more than a kind in the group that is made up of following each group:
In above-mentioned FL1 to FL38 or PL1 to PL59, * is connection portion, and wherein, connection portion can be connected with more than in the position of substitution in parantheses, and R1 to R16 is hydrogen independently of one another; Heavy hydrogen; Halogen; Amino; Itrile group; Nitro; With heavy hydrogen, halogen, amino, itrile group, the substituted or unsubstituted C of nitro
1~ C
40alkyl; C
2~ C
40thiazolinyl; C
1~ C
40alkoxyl group; C
3~ C
40cycloalkyl; C
3~ C
40heterocyclylalkyl; C
6~ C
40aryl; C
3~ C
40heteroaryl; C
3~ C
40aralkyl; C
3~ C
40aryloxy; C
3~ C
40arylthio or Si, more than 2 optional from R1 to R16 can be combined with each other and form ring, and can comprise S, N, O, Si.
5. luminescent quantum dot according to claim 1, is characterized in that,
Above-mentioned luminophore sends more than 400nm and is less than the light of 800nm wave band.
6. luminescent quantum dot according to claim 2, is characterized in that,
Above-mentioned linking group is selected from more than a kind in the group that is made up of mercaptan (thiol) base, carboxyl, amido, phosphine (phospine) base and phosphide (phosphide) base.
7. luminescent quantum dot according to claim 3, is characterized in that,
Above-mentioned spacer is substituted or unsubstituted saturated or unsaturated C
1~ C
30alkyl, C
3~ C
40cycloalkyl, Si
1~ Si
30silane.
8. luminescent quantum dot according to claim 3, is characterized in that,
Above-mentioned part is with one of in each structure of following each representation:
In above-mentioned each structure, the H part of-SH, COOH, NH is the part be combined with core/shell structures.
9. luminescent quantum dot according to claim 1, is characterized in that,
The grain of above-mentioned quantum dot is through being 5nm to 30nm.
10. a preparation method for luminescent quantum dot, prepares luminescent quantum dot according to claim 1, and the preparation method of described luminescent quantum dot is characterized in that,
The step stirred is carried out after being included in the solution being dispersed with core/shell structures the part added containing luminophore.
The preparation method of 11. luminescent quantum dot according to claim 10, is characterized in that,
Above-mentioned stirring carries out 0.1 to 100 hour at the temperature of normal temperature to 100 DEG C.
12. 1 kinds of luminous elements, is characterized in that,
Comprise luminescent quantum dot according to claim 1 and as luminophore.
The preparation method of 13. 1 kinds of luminous elements, is characterized in that,
Comprise the step forming luminescent layer with luminescent quantum dot according to claim 1.
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US20220416186A1 (en) * | 2019-11-19 | 2022-12-29 | Sharp Kabushiki Kaisha | Light-emitting element and light-emitting device |
JP2023509641A (en) * | 2020-01-08 | 2023-03-09 | ナノシス・インク. | Quantum dots with donor-acceptor ligands |
KR20220049682A (en) * | 2020-10-14 | 2022-04-22 | 삼성디스플레이 주식회사 | Quantum dot, and ink composition and light-emitting device and optical member and device including the same |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090087546A1 (en) * | 2007-09-28 | 2009-04-02 | Dai Nippon Printing Co., Ltd. | Process for producing electroluminescent device |
WO2012013272A1 (en) * | 2010-07-26 | 2012-02-02 | Merck Patent Gmbh | Quantum dots and hosts |
KR20120028670A (en) * | 2010-09-15 | 2012-03-23 | 삼성전자주식회사 | Quantum dot comprising resonant surface ligands, and organoelectroluminescent device and solar cell employing the same |
CN104603231A (en) * | 2012-08-29 | 2015-05-06 | 东进世美肯株式会社 | White light-emitting quantum dot |
-
2013
- 2013-12-03 CN CN201380062093.4A patent/CN104822798A/en active Pending
- 2013-12-03 US US14/649,235 patent/US20150315460A1/en not_active Abandoned
- 2013-12-03 KR KR1020130148953A patent/KR20140071256A/en not_active Application Discontinuation
- 2013-12-03 JP JP2015545378A patent/JP2016505661A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090087546A1 (en) * | 2007-09-28 | 2009-04-02 | Dai Nippon Printing Co., Ltd. | Process for producing electroluminescent device |
WO2012013272A1 (en) * | 2010-07-26 | 2012-02-02 | Merck Patent Gmbh | Quantum dots and hosts |
KR20120028670A (en) * | 2010-09-15 | 2012-03-23 | 삼성전자주식회사 | Quantum dot comprising resonant surface ligands, and organoelectroluminescent device and solar cell employing the same |
CN104603231A (en) * | 2012-08-29 | 2015-05-06 | 东进世美肯株式会社 | White light-emitting quantum dot |
Non-Patent Citations (1)
Title |
---|
A.KHETUBOL ET AL: "Blue light-emitting-diodes from Poly (N-vinylcarbazole) doped with colloidal quantum dots encapsulated with carbazole terminated ligand:Spectroscopic studies and Devices", 《PROC. OF SPIE》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106252530A (en) * | 2016-10-11 | 2016-12-21 | 赛特斯信息科技股份有限公司 | A kind of QLED method for packing isolating water oxygen |
CN110828681A (en) * | 2018-08-14 | 2020-02-21 | 乐金显示有限公司 | Quantum dot light emitting device and display device comprising same |
CN110828681B (en) * | 2018-08-14 | 2022-06-28 | 乐金显示有限公司 | Quantum dot light emitting device and display device comprising same |
US11393990B2 (en) | 2018-08-14 | 2022-07-19 | Lg Display Co., Ltd. | Quantum dot light emitting device and display apparatus including the same |
CN112397620A (en) * | 2019-08-19 | 2021-02-23 | Tcl集团股份有限公司 | Nano composite particle and preparation method and application thereof |
CN112397620B (en) * | 2019-08-19 | 2022-02-18 | Tcl科技集团股份有限公司 | Nano composite particle and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
JP2016505661A (en) | 2016-02-25 |
US20150315460A1 (en) | 2015-11-05 |
KR20140071256A (en) | 2014-06-11 |
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